Catalytic compositions based on compounds of rhenium and aluminium, preparation thereof and use thereof for the metathesis of olefins

Abstract

The present invention concerns new catalytic compositions containing at least one compound of rhenium and aluminium corresponding to the general formula: O 3 Re--O-- Al(OR)(L) x --O! n --ReO 3 in which R is a hydrocarbyl residue, for example alkyl, cycloalkyl, alkenyl, aryl and aryl or cycloalkyl which are substituted, containing from 1 to 40 carbon atoms, which residue can be substituted by alkoxy groups or by halogens, L is the synthesis solvent, x is equal to 0 or 1 and n is an integer of from 1 to 10. The invention also concerns the preparation of such compositions and the use thereof for the metathesis of olefins in a homogeneous phase.

I claim: 
     
       1. A catalyst composition comprising at least one unsupported rhenium/aluminum compound of the formula:   O.sub.3 Re--O-- Al(OR)(L).sub.x --O!.sub.n --ReO.sub.3     wherein R is aryl of up to 40 carbon atoms, optionally substituted by alkyl, alkoxy or halogen, n is an integer of from 1 to 10, x is equal to 0 or 1 and L represents synthesis solvent.   
     
     
       2. A composition according to claim 1 wherein R is alkyl, cycloalkyl, alkenyl, or and aryl or cycloalkyl optionally substituted by at least one alkyl group. 
     
     
       3. A composition according to claim 1, wherein R is alkyl, cycloalkyl, alkenyl, aryl, or aryl or cycloalkyl optionally substituted by at least one alkyl group, each being substituted by at least one alkoxy group or at least one halogen. 
     
     
       4. A composition according to claim 1, wherein R contains from 2 to 30 carbon atoms. 
     
     
       5. A composition according to claim 1, wherein R is ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclohexyl, benzyl, diphenylmethyl, phenyl, 2-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-t-butylphenyl, 2-t-butyl-4-methylphenyl, 2,6-di-t-butylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,4,6-tri-t-butylphenyl, 2-phenylphenyl, 2,6-diphenylphenyl, 2-fluorophenyl, 4-fluorophenyl or pentafluorophenyl. 
     
     
       6. A composition according to claim 1, wherein L is an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, an ether or a sulphide. 
     
     
       7. A composition according to claim 1, further comprising a solvent L 1 . 
     
     
       8. A composition according to claim 7, wherein the solvent L 1  is an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon or a nitro derivative. 
     
     
       9. A process for the preparation of a catalytic composition according to claim 1, comprising reacting rhenium heptoxide with at least one compound of aluminum of the formula (RO) q  AlR' r  wherein R is a hydrocarbyl residue containing from 1 to 40 carbon atoms, R' is an alkyl residue containing from 1 to 20 carbon atoms and q and r are equal to 1 or 2 in such a way that the sum q+r is equal to 3, the molar ratio between the aluminum compound and the rhenium being between 0.2:1 and 10:1 and the reaction taking place in a solvent L which an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, an ether or a sulphide, the reaction temperature being between -80° and +100° C. 
     
     
       10. A process for the preparation of the catalytic composition according to claim 1, comprising reacting rhenium heptoxide with at least one compound of the formula AlR'3 in which R' is an alkyl residue containing from 1 to 20 carbon atoms, and with at least one compound of the formula ROH, R being hydrocarbyl residue containing from 1 to 40 carbon atoms, the reaction occurring in a solvent L. 
     
     
       11. A preparation process according to claim 9, wherein said solvent L is anhydrous. 
     
     
       12. A preparation process according to claim 9, wherein, at the end of the reaction, the solvent is at least partially removed and the residue is extracted by another solvent L 1 . 
     
     
       13. A preparation process according to claim 12, wherein the solvent L 1  is an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, an ether or a nitro derivative. 
     
     
       14. A process for the metathesis of olefins, comprising subjecting such olefins to a temperature of between -20° and +200° C. at a pressure such that the reactants are maintained at least in respect of the majority thereof in the liquid phase, in the presence of a catalytic composition obtained in accordance with claim 1. 
     
     
       15. A process according to claim 14 wherein the temperature is between 0° and 100° C. 
     
     
       16. A process according to claim 14, wherein the olefins are monoolefins having from 2 to 30 carbon atoms, cycloolefins having from 3 to 20 carbon atoms, polyolefins having from 4 to 30 carbon atoms, cyclopolyolefins having from 5 to 30 carbon atoms, monoolefins having from 2 to 30 carbon atoms and bearing halogen or ester functional groups, or polyolefins having from 4 to 30 carbon atoms and bearing halogen or ester functional groups. 
     
     
       17. A process according to claim 14, wherein the olefins are ethylene, propylene, butenes, pentenes, cyclopentene, cyclooctene, norbornene, hexa-1-4-diene, octa-1-7-diene, cycloocta-1,5-diene, norbornadiene, dicyclopentadiene or methyl oleate. 
     
     
       18. A process according to claim 14, conducted in the presence of at least one co-catalyst having alkylating and/or Lewis acid properties. 
     
     
       19. A process according to claim 18, wherein said catalyst is an aluminum compound, a boron compound, a gallium compound, a tin compound or a lead compound. 
     
     
       20. A process according to claim 19, wherein said co-catalyst is aluminum trichloride, aluminum tribromide, dichloroethylaluminum, chlorodiethylaluminum, triethylaluminum, methylaluminoxane, isobutylaluminoxane, boron trifluoride, gallium trichloride, gallium tribromide, tetramethyltin, tetraethyltin, tetrabutyltin or tetraethyl lead. 
     
     
       21. A composition according to claim 5, wherein R is benzyl, diphenylmethyl, phenyl, 2-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-t-butylphenyl, 2-t-butyl-4-methylphenyl, 2,6-di-t-butylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,4,6-tri-t-butylphenyl, 2-phenylphenyl, 2,6-diphenylphenyl, 2-fluorophenyl, 4-fluorophenyl or pentafluorophenyl. 
     
     
       22. A composition according to claim 1, which is homogeneous. 
     
     
       23. A composition according to claim 1, which is in liquid phase.